Synlett 2010(17): 2617-2620  
DOI: 10.1055/s-0030-1258576
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Isomerization of Electron-Poor Alkynes to the Corresponding (E,E)-1,3-Dienes Using a Bifunctional Polymeric Catalyst Bearing Triphenylphosphine and Phenol Groups

Cathy Kar-Wing Kwong, Michael Yunyi Fu, Henry Chun-Hin Law, Patrick H. Toy*
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. of China
Fax: +85228571586; e-Mail: phtoy@hku.hk;
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Publikationsverlauf

Received 28 July 2010
Publikationsdatum:
23. September 2010 (online)

Abstract

The use of a bifunctional non-cross-linked polystyrene bearing both phosphine and phenol groups for the organocatalytic isomerization of alkynes bearing electron-withdrawing ester substituents to afford the corresponding (E,E)-dienes in excellent yield and stereoselectivity is described. When polystyrene functionalized with only phosphine groups was used as the catalyst, either low or no yield of the desired product was obtained. Thus both of the functional groups of the bifunctional polystyrene catalyst were essential for efficient catalysis to occur. This bifunctional polymeric catalyst was also used to synthesize (E,E,E)-trienes and (E,E)-diene-substituted 2(H)-pyran-2-ones from the corresponding alkynes.

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We have previously reported the use of a cross-linked bifunctional analogue of 1 as a catalyst in Morita-Baylis-Hillman reactions, which have some mechanistic similarities to the isomerization reactions reported herein. However, due to its heterogeneous nature and poor swelling properties, it was less efficient than a corresponding cross-linked monofunctional analogue of 2. See ref. 8d for details.

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See Supporting Information for details.